Tris-mercapto-s-trioxanes and trithanes



United States Patent Oflice Patented Nov. 12, 1968 3,410,869 TRIS-MERCAPTO-S-TRIOXANES AND TRITHANES Elliot Bergman, Modesto, 'Calif., and William De Acetis,

New York, N.Y., assignors to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 284,365, May 31, 1963. This application Oct. 17, 1966, Ser. No. 586,960

Claims. (Cl. 260-327) ABSTRACT OF THE DISCLOSURE Disclosed in the application are new polymercaptans comprising heterocyclic compounds substituted in at least three different places on the ring with radicals containing a mercapto group, such as a tris(mercaptoalkyl) trioxane. Also disclosed are methods for making the new compounds by forming a thioester of the corresponding poly- (chloroalkyl) compound and reacting it with ammonia, or by reacting the chloroalkyl compound with sodium bisulfide under hydrogen sulfide pressue. Uses of the new polymercaptans, particularly as curing agents for epoxy resins, are also disclosed.

This application is a continuation-in-part of our application Ser. No. 284,365, filed May 31, 1963, now US. Patent 3,297,635.

This invention relates to new sulfur-containing compounds and to their preparation. More particularly, the invention relates to new polymercaptans possessing more than two-SH groups which are particularly valuable as curing agents for polyepoxides, and to a method for preparing the new polymercaptans.

Specifically, the invention provides new and particularly useful polymercaptans comprising heterocyclic compounds substituted in at least three different places on the ring with radicals containing a mercapto group such as, for example, tris(mercaptoalkyl) trioxanes.

As a special embodiment, the invention provides a process for preparing the new polymercaptans by reacting a polychlolrinated heterocyclic compound with an alkali metal salt of a thioalkanoic acid or thiourea and then converting the resulting product into the desired heterocyclic poly mercaptan. The invention further provides a method for making the new products by reacting the polychlorinated compound with sodium bisulfide under hydrogen sulfide pressure.

As a further special embodiment, the invention provides a method for using the above-described polymercaptans for curing polyepoxides which comprise mixing and reacting the polyepoxide which contains more than one vie-epoxy group with one or more of the above-described polymercaptans, preferably in the presence of an activator, such as tertiary amine.

Polyepoxides, such as, for example, those obtained by reacting epichlorohydrin with polyhydric phenols in the presence of caustic, are promising materials for use in many industrial applications as they can be reacted with curing agents to form insoluble infusible products having good chemical resistance. The conventional polyepoxidecuring agents systems, however, have certain drawbacks that have limited their use for certain applications. For example, the known systems take considerable time to cure at low temperatures. With the best aliphatic type amine curing agents, the systems take several hours to set to a hard product. Because of this, it has been difficult to use the polyepoxide systems for applications, such as highway coatings, maintenance surface coating and the like, where the coating must dry in a very short time.

It has been found that certain types of polymercaptans can be used to cure the polyepoxides at a rapid rate at the low temperatures. The use of these materials has been limited, however, because they have a strong odor, in some cases are toxic, and in most cases are very thick liquids or solids which are difiicult to mix with the polyepoxides.

It is an object of the invention, therefore, to provide a new group of sulfur-containing compounds which are good curing agents for polyepoxides. ][t is a further object to provide new heterocyclic polymercaptans and a method for their preparation. It is a further object to provide new heterocyclic polymercaptans that can cure polyepoxides at a low temperature in a short period. It is a further object to provide new polymercaptans that have little or no odor. It is a further object to provide new heterocyclic polymercaptans that are substantially nontoxic and are easily handled as liquids. It is a further object to provide new heterocyclic polymercaptans that have a functionality of at least three and can be used for a variety of important polymerization reactions. These and other objects of the invention will be apparent from the following detailed description thereof.

It has now been discovered that these and other objects may be accomplished by the new polymercaptans of the present invention which comprise heterocyclic compounds substituted on at least three different elements in the ring with radicals containing a -SH group such as, for example, tris(mercaptoalkyl) trioxane. It has been surprisingly found that these compounds are particularly effective for the cure of polyepoxides when used at the lower'reaction temperature such as, for example, from 0 C. to about 20 C, preferably when used in combination with the accelerators as described hereinafter. Further, the cured products are hard and tough and have excellent resistance to water, solvents, and alkalii. Further advantage is found in the fact that the new curing agents are substantially free of the characteristic mercaptan odor and can be used in open or closed spaces without any great deleterious effect. Further, the new products are substantially nontoxic and there is no great danger of skin irritation and the like when ordinary sanitary precautions are employed. Many of the new polymercaptans are fluid liquids and can be used directly in the polyepoxide composition without the addition of solvents or diluents. This was quite surprising to find that such highly functional polymercaptans could be obtained in this physical state.

The new polymercaptans of the present invention comprise the heterocyclic compounds which are substituted on at least three different elements in the ring with a radical containing a mercapto group. The compounds are preferably mononuclear but may contain two or more ring structures which may be separate or joined together. The mercapto groups are preferably not more than 6 carbon atoms removed from the ring. In. addition, the rings are preferably 5 to 7 membered rings and preferably con- 3 4 tain in addition to carbon, a heteroatom such as oxygen, and sulfur, nitrogen, phosphorous and the like.

Examples of these compounds include, among others, CH3 the trioxanes, trithianes, dioxathianes, o radithianes, oxa- |(JHKCHZSH 211168, triazines, thiazines, dithiazines, dioxarsenoles, ox- 5 (l J) athiazoles, dithiazoles, triazoles, dioxalanes, isoxazoles, isothiazoles, dioxaborines, dioxazines, thiadiazines, and the like, which have at least three mercapto-substituted CHzSH radicals attached to the said rings.

Specific examples of these include, among others: Also included in the above are the polymeric poly- 2,4,6-tris(beta-mercaptoethyl) 1,3,5-trioxane; mercaptans as obtained by joining two or more of the 2,4,6-tris(beta-mercaptoethyl) 1,3,5-trithiane; above compounds together as H CH 0\ 0 o 0 o (HSCHgCH2)z-l I +(CHgHaSH); CH HCCH2CHaSCH2CH:CH HO 2,4,6-tris(mercaptomethyl) 1,3,5-trioxane; or by coupling reactions with dialdehydes and the like. 2,4,6-tris(mercaptornethyl) 1,3,5-trithiane; Preferred members of the above group comprises the 2,4,6-tris(beta-mercaptoethyl) 1,3-dioxa-5-thiane; heterocyclic polymercaptans of the general formula 2,4,6-tris(beta-mercaptoethyl) loxa-3,5-dithiane; 2,4,5-tris( beta-mercaptoethyl) 1,3-dioxalane;

2,4,5-tris(mercaptomethyl) 1,3-dioxalane; 2,4,6-tris(alpha-methyl-beta-mercaptoethyl) 1,3,5-tri- X X oxane; I +(RSHM 2,4,6-tris(beta-methyl-beta-mercaptoethyl) 1,3,5-trithiane; X X 2,4,6-tris(beta-mercaptobutyl) 1,3,5-trioxane; 2,4,6-tris(beta-mercaptohexyl) 1,3,5-trithiane; X 2,4,6-tris(beta-phenyl-beta-mercaptoethyl) 1,3,5-trioxane; 2,4,6-tr1s(beta-cyclohexyl-beta-mercaptoethyl) 1,3,5-tri wherein at least one X is a member of the group com f sisting of oxygen, sulfur and nitrogen, and the remaining 2,4,6-tr mercapto l,3,5-tr ox ane, Xs are carbon atoms which when not attached to the 2,2,6-tqmercapto 1,3,5-trith1ane, 4O mercaptan-containing radical are attached in the remain- 2, ,6-tr s(l-th1a-4-mercaptobutyl) 1,3,5-tr1oxane, ing valences to members of the group consisting of hydro- 246'trfs(loxa'4mercaptobutyl) li3isjtnoxanei gen, halogen and alkyl radicals, and R is a bivalent 2,3,6-tr1s(beta-mercaptoethyl) 1,4-oxaz1ne; hydrocarbon radioaL 246'trfs(3'mercaptopropyl) i 'ff Particularly preferred polymercaptans are those of the 2,4,6-tr1s(mercaptornethyl) 1,3,5-tr1aZ1ne; f 1

ormu a 2,4,6-tr1s(beta-mercaptoethyl) 1-th1a-3,5-d1az1ne and C-RSH HSCHzCH:-C CH-CHa-CHa-SH z Z Esta-4 2E Hil-RSH oHicHzsH I 2CHzSH g wherein Z is a member of the group consisting of oxygen, 0 O sulfur and nitrogen and R is a bivalent hydrocarbon HSCHZCHZAEH H('3 OH2OH2 sH radical, preferably containing from 1 to 6 carbon atoms.

\ Of special interest are the poly(mercaptoalkyl) tri- I oxanes, poly(mercaptoalkyl) trithianes, the poly(mercap- CHZOHflSH toalkyl) triazines and combinations thereof, such as the poly(mercaptoalkyl) thiadioxanes, wherein the alkyl groups contain from 1 to 5 carbon atoms.

Of particular interest are the cycloaliphatic acting (i.e., non-aromatic) heterocyclic oxygen-containing and H sulfur-containing products and especially those derived 6 by trimenzation, cotn'merization, tetramerization, coand O tri-tetramerization of chlorinated aldehydes and then con- C-C-S-C-C-SH meeting to the mercapto derivative as noted below.

SH S The polymercaptans of the present invention can be prepared by a variety of methods. They may be prepared, H('3-CH2 for example, by reacting the corresponding chloride com- 0 pound with an alkali metal salt of a thioalkanoic acid, such as sodium thioacetic acid and then refluxing the resulting thioester with methanol or ammonia to form the mercaptan product. This reaction may be illustrated SH SH 0 SH SH by the following equation showing the preparation of 2,4,6-tris(beta-mercaptoethyl) 1,3,5-trioxane from 2,4,6- tris(beta-chloroethyl) 1,3,5-trioxane:

CHnCHgCI 0 ornoosm olornom-i j-cmomol OHflCN OHzOHzSH The starting material in the above reaction are those compounds as described above wherein a halogen replaces the mercapto group. The preferred halogenated compounds of this type are preferably obtained by the trimerization, tetrarnerization of halogenated aldehydes, such as chloropropionaldehyde, chloroacetaldehyde, dichloropropionaldehyde and the like. In making these, one may use the same or mixture of aldehydes, or mixtures with nonhalogen-containing aldehydes.

The alkali metal salt of a thioalkanoic acid employed in the reaction is preferably a sodium salt, such as sodium thioacetate. This salt is employed in at least one molar amount for every halogen atom to be converted, and preferably in an excess, such as up to 30 or 40% excess of the theoretical amount.

The reaction may be accomplished with or without solvents or diluents, but it is generally preferred to utilize solvents, such as acetonitrile, tetrahydrofuran, dimethyl formamide, dimethyl sulfoxide, methanol and the like.

The reaction with the alkali metal salt is preferably accomplished by applying heat, with preferred temperatures varying from about 50 to 100 C. In general, it is preferred to conduct the reaction at reflux temperature.

The resulting thioesters may be recovered as such before conversion to the mercaptan derivative or they may be further treated without recovery. The thioesters may be recovered by filtration to remove the salt formed in the reaction, and then extracted or stripped to remove the solvents or diluents employed in the reaction mixture. When recovered, the thioesters appear as fluid liquids to crystalline solids. They possess at least three thioester groups, i.e.,

SCR

groups and can be utilized in various applications, such as plasticizers, etc., in addition to their use as intermediates for the preparation of the polymercaptans.

The thioester can be converted to the mercaptan by any suitable method. One method comprises reacting the thioester with alcohol or with ammonia. The preferred method comprises reacting the thioester with at least an equivalent amount of alcohol, such as methanol, i.e., at least one mole of alcohol per thioester group to be converted. This reaction is preferably accomplished by application of heat, e.g., temperatures ranging from about 50 to 100 C., and still more preferably at the reflux temperature. If ammonia is employed, it is preferably bubbled into an alcohol solution of the thioester and the mixture allowed to stand at room temperature for several hours.

The desired polymercaptan can be recovered from the reaction mixture by any suitable method, such as extraction, distillation, and the like. It is generally preferred to strip out the solvent to obtain the heterocyclic polymercaptan.

The new polymercaptans can also be prepared by other suitable methods. One additional method comprises reacting the corresponding halogen-substituted heterocyclic compound with sodium bisulfide under hydrogen sulfide pressure. The sodium bisulfide is preferably employed in excess of that needed to convert the halogen atoms, and is preferably used in amounts varying from about 2 to 5 times the amount needed for conversion. The reaction with sodium bisulfide is preferably accomplished in the presence of a solvent or diluent, such as ethanol, methanol or mixtures of alcohols with water. The temperature employed for the reaction will preferably vary from about 50 to 120 C. with a preferred range varying from about to C. The pressure of the hydrogen sulfide preferably varies from about 200 to 600 p.s.i.g. In recovering the desired product, the hydrogen sulfide pressure is released, the product neutralized with acetic acid and the mixture stripped of solvent and subsequently distilled to give the desired heterocyclic polymercaptan.

Another less preferred method comprises reacting the halogenated derivative with thiourea in a solvent, such as ethanol, and then reacting the resulting product with ammonia to convert the thiouronium salt to the desired polymercaptan. The conversion may also be accomplished by a special technique of reacting the thiouronium salt with sodium bisulfide or sodium sulfide.

The new heterocyclic polymercaptains of the present invention are fluid to viscous liquids or solids. They have active mercapto groups and at least three per molecule. They are generally free of odor and. substantially nontoxic. They are soluble in conventional solvents, such as benzene, aliphatic hydrocarbons, ethers, esters and the like. They are also compatible with conventional resins, tars, oils, polymers, and the like, such as asphalts, coal tars, rosin, phenol-formaldehyde resins, vinyl polymers, and particularly epoxy resins.

As noted above, they are particularly useful and valuable as curing agents for the polyepoxides.

The polyepoxides to be used in the process of the invention comprise those materials possessing more than one vicinal epoxy group, i.e., more than one group. These compounds may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted with substituents, such as chlorine, hydroxyl groups, other radicals and the like. They may be monomeric or polymeric.

For clarity, many of the polyepoxides and particularly those of the polymeric type are described in terms of epoxy equivalent values. The meaning of this expression is described in US. 2,633,458. The polyepoxides used in the present process are those having an epoxy equivalency greater than 1.0.

Various examples of polyepoxides that may be used in the process of the invention are given in US. 2,633,458 and it is to be understood that so much of the disclosure of that patent relative to examples of polyepoxides is incorporated by reference into this specification.

Other examples include the epoxidized esters of the polyethylenically unsaturated monocarboxylic acids, such as epoxidized linseed, soybean, perilla, oiticia, tung, Walnut, and dehydrated castor oil, methyl linoleate, butyl linoleate, ethyl 9,12-octadecadienoate, butyl 9,l2,l5-octadecatrienoate, butyl eleostearate, monoglycerides of tung oil fatty acids, monoglycerides of soybean oil, sunflower rapeseed, hempseed, sardine, cottonseed oil and the like.

Another group of the epoxy-containing materials used in the process of the invention include the epoxidized esters of unsaturated monohydric alcohols and polycarboxylic acids, such as, for example,

di(2,3-epoxybutyl) adipate, di(2,3-epoxybutyl) oxalate, di(2,3-epoxyhexyl) succinate, di(3,4-epoxybutyl) maleate, di(2,3-epoxyoctyl) pimelate, di(2,3-epoxybutyl) phthalate, di(2,3-epoxyoctyl) tetrahydrophthalate, di(4,5-epoxydodecyl) maleate, di(2,3-epoxybutyl) terephthalate, di(2,3-epoxypentyl) thiodipropionate, di(5,6-epoxytetradecyl) diphenyldicarboxylate, di(3,4-epoxyheptyl) sulfonyldibutyrate, tri(2,3-epoxybutyl) l,2,4-butanetricarboxylate, di(5,6-epoxypentadecyl) tartarate, di(4,5-epoxytetradecyl) maleate, di(2,3-epoxybutyl) azelate, di(3,4-epoxybutyl) citrate,

di(5,6-epoxyoctyl) cyclohexane-l,Z-dicarboxylate, di(4,5-epoxyoctadecyl) malonate.

Another group of the epoxy-containing materials includes those epoxidized esters of unsaturated alcohols and unsaturated carboxylic acids, such as 2,3-epoxybutyl 3,4-epoxypentanoate,

3,4-epoxyhexyl 3,4-epoxyhexyl 3,4-epoxypentanoate,

3,4-epoxycyclohexyl 3,4-epoxycyclohexonate,

3,4-epoxycyclohexyl 4,5-epoxyoctanoate,

2,3-epoxycyclohexylmethyl epoxycyclohexane carboxylate.

Still another group of the epoxy-containing materials include epoxidized derivatives of polyethylenically unsaturated polycarboxylic acids such as, for example,

dimethyl 8,9,l2,13-diepoxyeicosanidioate,

dibutyl 7,8,1l,l2-diepoxyoctadecanedioate,

dioctyl 10,1l-diethyl-8,9,l2,l3-diepoxyeic0nsanedioate,

dihexyl 6,7,l0,l1-diepoxyhexadecanedioate,

didecyl 9-epoxyethyl-10, l l-epoxyoctacanedioate,

dibutyl 3-butyl-3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate,

dicyclohexyl 3,4,5 ,6-diepoxycyclohexane-1,2-dicarboxylate,

dibenzyl 1,2,4,5-diepoxycyclohexane-1,2-dicarboxylate and diethyl 5,6,10,1l-diepoxyoctadecyl succinate.

Still another group comprises the epoxidized polyesters obtained by reacting an unsaturated polyhydric alcohol and/or unsaturated polycarboxylic acid or anhydride groups, such as, for example, the polyester obtained by reacting 8,9,12,13-eicosanedienedioic acid with ethylene glycol, the polyester obtained by reacting diethylene glycol with 2-cyclohexane-1,4-dicarboxylic acid and the like, and mixture thereof.

Still another group comprises the epoxidized polyethylenically unsaturated hydrocarbons, such as epoxidized 2,2-bis(2-cyclohexenyl)propane, epoxidized vinyl cyclohexene and epoxidized dimer of cyclopentadiene.

Another group comprises the epoxidized polymers and copolymers of diolefins, such as butadiene. Examples of this include, among others, butadiene-acrylonitrile copolymers (Hycar rubbers), butadiene-styrene copolymers and the like.

Another group comprises the glycidyl containing nitrogen compounds, such as diglycidyl aniline and diand triglycidylamine.

The polyepoxides that are particularly preferred for use in the compositions of the invention are the glycidyl ethers and particularly the glycidyl ethers of polyhydric phenols and polyhydric alcohols. The glycidyl ethers of polyhydric phenols are obtained by reacting epichlorohydrin with the desired polyhydric phenols in the presence of alkali. Polyether A and Polyether B described in the above-noted US. 2,633,458 are good examples of polyepoxides of this type. Other examples include the polyglycidyl ether of l,1,2,2-tetrakis(4-hydroxyphenyl)ethane (epoxy value of 0.45 eq./100 g. and melting point C.), polyglycidyl ether of l,1,5,5-tetrakis(hydroxyphenyl) pentane (epoxy value of 0.514 eq./ g.) and the like and mixtures thereof.

The amount of new polymercaptans to be employed in the cure of the polyepoxide may vary within certain limits. In general, the polyepoxides are combined with at least .8 equivalents of the polymercaptan. As used herein equivalent amount refers to that amount needed to furnish one SH group per epoxy group to be reacted. Preferably the polymercaptans and polyepoxides are combined in chemical equivalent ratios vary from .8:l.5 to 1.5 :8.

It is preferred in some cases to employ activators for the cure. Examples of these include, among others, phenols, sulfides, mercaptans, organic phosphines, organic arsines, organic antimony compounds, amines, amine salts or quaternary amonium salts, etc. Preferred activators are the phenols, phosphines, arsines, amines, and sulfides, such as, for example, benzyldimethylamine dicyandiamide p,p-bis(dimethylaminophenyl) methane, pyridine, dimethyl aniline, dimethylethanolamine, methyldiethanolamine, morpholine, dimethylaminopropylamine, dibutylaminopropylamine, stearyl dimethylamine, tri-n-butyl amine, N,N-dibutyl butylamine, tri-n-hexylamine, ethyl di-n-propylamine, phenylene diamine, diethylene triamine, dibutyl sulfide, dicotyl sulfide, dicyclohexyl sulfide and the like, and mixtures thereof. The salts may be exemplified by the inorganic and organic acid salts of the amines, such as, for example, the hydrochloride, sulfate and acetate of each of the above-described tertiary amines. The quaternary ammonium salts may be exemplified by the following: benzyltrimethylammonium chloride, phenyltributylammonium chloride, cyclohexyltributylammonium sulfate, benzyltrimethylammonium sulfate, benzyltrimethylammonium borate, diphenyldioctylammonium chloride, and the like and mixtures thereof.

Preferred activators to be used are the sulfides, phosphines and tertiary amines, and more preferably the monoand diamines wherein the amine hydrogens have been replaced by aliphatic, cycloaliphatic or aromatic hydrocarbon radicals containing not more than 15 carbon atoms such as, for example, the trialkyl amines, triaryl amines, triarylalkylamines, alkyl arylalkylamines, tricycloalkylamines, alkyl dicycloalkylamines, diaminoalkanes, dialkylene triamines, phenylene diamines and di(aminoaryl)' alkanes. Preferred amine salts are the hydrochloride, sulfate and acetate of the above-described preferred amines. The preferred quaternary salts are those of the formula wherein Y is nitrogen, R is an alkyl, aryl or arylalkyl radical, preferably containing no more than 12 carbon atoms and X is chlorine.

The activators noted above are generally employed in amounts varying from 0.1 part to 4 parts per 100 parts of polyepoxide, and preferably from 1 part to 3 parts per 100 parts of polyepoxide.

In curing the polyepoxides, it is usually desirable to have the polyepoxide in a mobile condition when the polymercaptan is added in order to facilitate mixing. The polyepoxides, such as the glycidyl polyether of polyhydric phenols, are generally very viscous to solid materials at ordinary temperature. With those that are liquid, but too viscous for ready mixing, they are either heated to reduce the viscosity, or have a liquid solvent added thereto in order to provide fluidity. Normally solid members are likewise either melted or mixed with a liquid solvent.

Various solvents are suitable for achieving fluidity of the polyepoxide. These may be volatile solvents which escape from the polyepoxide compositions containing the adduct by evaporation before or during the curing such as, esters such as ethyl acetate, butyl acetate, Cellosolve acetate (ethylene glycol monoacetate), methyl Cellosolve acetate (acetate ethylene glycol monomethyl ether), etc., ether alcohols, such as methyl, ethyl, or butyl ether of ethylene glycol or diethylene glycol; chlorinated hydrocarbons such as trichloropropane, chloroform, etc. To save expense, these active solvents may be used in admixture with aromatic hydrocarbons such as benzene, toluene, xylene, etc., and/or alcohols such as ethyl, isopropyl, or n-butyl alcohol. Solvents which remain in the cured compositions may also be used, such as diethyl phthalate, dibutyl phthalate and the like, as well as cyano-substituted hydrocarbons, such as acetonitrile, propionitrile, adiponitrile, benzonitrile, and the like. It is also convenient to employ a polyepoxide, such as one of the glycidyl polyethers of the dihydric phenol, in admixture with a normally liquid glycidyl polyether of a polyhydric alcohol. In fact, two or more of any of the polyepoxides may be used together as mixtures. In such a case, the amount of the adduct added and commingled is based on the average epoxide equivalent weight of the polyepoxide mixture.

Various other ingredients may be mixed with the polyepoxide subjected to cure with the novel adducts including pigments, fillers, dyes, plasticizers, resins, and the like.

The polyepoxides may be cured with the new polymercaptans by merely mixing the two components together, preferably in the presence of the above-noted activators. The cure time may vary from a few minutes to a few hours, depending on the type and quantity of reactants and presence of catalyst. In general, in the presence of activators, the cure takes place readily at room temperature. Fast reaction may be obtained, of course, by applying heat. Preferred temperatures range from about 20 to 200 C. With small castings, it is preferred to cure at room temperature and then post cure for a few hours at elevated temperatures, say 40 C. to 170 C.

One important application of the use of the new polymercaptans as curing agents for polyepoxides is in the reparation of laminates or resinous particles reinforced with fibrous textiles. Although it is generally preferred to utilize glass cloth for this purpose, any of the other suitable fibrous materials in sheet form may be employed such as glass matting, paper, asbestos paper, mica flakes, cotton bats, duck muslin, canvas, and the like. It is useful to prepare the laminates from woven glass cloth that has been given prior treatment with well-known finishing or sizing agents therefor, such as chrome methacrylate or vinyl trichlorosilane.

In preparing the laminate, the sheets of fibrous materials are preferably first impregnated with the mixture of the polyepoxide, polymercaptan and activator. This is conveniently accomplished by dissolving the polymercaptan in a solvent and mixing the solution with the polyepoxide so as to obtain a fluid mixture. The sheets of fibrous material are impregnated with the mixture by spreading it thereon or by dipping or otherwise immersing them in the impregnant. The solvent is conveniently removed by evaporation and the mixture is cured by the application of heat. A plurality of the impregnated sheets can be superimposed and the assembly cured in a heated press under a pressure of about 25 to 500 or more pounds per square inch. The resulting laminate is extremely strong and resistant against the action of organic and corrosive solvents.

The new compositions of the invention are particularly outstanding as adhesives. In this application they can be used as a paste or solution depending on the method of preparation as described above. Other materials may also be included in the composition, such as pigments, plasticizers, stabilizers, and reinforcing fillers, such as aluminum powder, asbestos, powdered mica, zinc dust, Bentonite, ground glass fibers, Monetta clay and the like. These fillers are preferably used in amounts varying from about 10 parts to 200 parts per parts of the polyepoxide and polymercaptan compound. Other materials that may be included include other types of resins, such as phenol-aldehyde resins, urea-aldehyde resins, furfural resins, polyacetal resins, carbonate resins, polyamide resins, and the like.

The compositions may be used in the bonding of a great variety of different materials, such as metal-to'metal to other materials, such as plastic, wood-to-wood, glassto-glass, glass-to-metal, and the like. They are of particular value, however, in the bonding of metals such as aluminum-to-alurninum and steel-to-steel. When applied as an adhesive, the compositions may simply be spread on the desired surface to form films of various thicknesses, e.g., 0.5 mil to 30 mils, and then the other surface superimposed and heat applied. Curing pressure can be light contact pressures up to about 500 p.s.i.

When the compositions are used as adhesives for metalto-metal bonding, it has sometimes been found advantageous to impregnate cotton, rayon, synthetic fiber or glass cloth textiles with the compositions, and then use the impregnated textiles as a bonding tape for joining the metals. Such tapes provide convenient means for handling and using the compositions in adhesive applications. The tape is inserted between two metals desired to be joined, and the assembly is heated and baked to cure the resin whereby articles are obtained wherein the joined surfaces have not only excellent strength at ordinary temperatures, but also retain good strength even through heated at quite elevated temperatures for long periods of time. A preferred tape for such use comprises a glass fiber textile impregnated or coated with a mixture of the polyepoxide, phthalocyanine compound and atomized aluminum powder or dust.

To illustrate the manner in which the invention may be carried out, the following examples are given. It is to be understood, however, that the examples are for the purpose of illustration and that the invention is not to be regarded as limited to any of the specific conditions or reactants recited therein. Unless otherwise specified, parts described in the examples are parts by weight. The polyethers referred to herein by letter are those described in US. 2,633,458.

Example I This example illustrates the preparation and properties of 2,4,6-tris(beta-mercaptoethyl) 1,3,5-trioxane and the intermediate trithiolacetate derivative.

136.8 parts of beta-chloropropionaldehyde trimer, 193.1 parts of sodium thiolacetate and 587.0 parts of acetonitrile were added to a reaction flask and refluxed for 3 hours (pot temp. 87 C.) with agitation under nitrogen. The reaction mixture was then filtered to remove salts. The filtrate was stripped and stabilized at 40 C./l mm. The product (93% yield) was a dark, viscous oil identified as the tris-thiolacetate derivative Analysis.-Theory: C, 45.4%; H, 6.06%; S, 24.3%. Found: C, 45.1%; H, 6.1%; S, 24.7%.

14.7 parts of the above-noted thiolacetate was dissolved in 100 parts of absolute alcohol. Ammonia was bubbled into the reaction mixture overnight at .room temperature. The mixture was stripped, filtered, and dried. The product I I (84% yield) was a fluid liquid identified as 2,4,6-tris(betamercaptoethyl) 1,3,5-trioxane:

Analysis. Theory: c, 40.0%; H, 6.7%; s, 35.6%. Found: C, 41.0%; H, 6.7%; S, 34.0%. Mercaptan, 0.98 eq./l g.; theory, 1.11 eq./l00 g.

Example II This example illustrates the preparation and properties of 2,4,6-tris(mercaptomethyl) 1,3,5-trioxane.

95.5 parts of 2,4,6-tris(chloromethyl) 1,3,5-trioxane prepared by trimerization of chloroacetaldehyde was dissolved in 500 parts of acetonitrile. This mixture along with 162 parts of sodium thiolacetate was charged to a reaction flask equipped with stirrer, thermometer and nitrogen inlet. The mixture was brought to reflux under nitrogen and agitated at that temperature for about 50 hours. The reaction mixture was then added to an ether/ water mixture. The organic layer was removed and washed. The organic phase was then dried, filtered and stripped at 40 C. 2-3 mm. to yield 113 parts of a light tan solid. Analysis of the recrystallized product, M.P. 106; indicated it to be the tris-thiolacetate.

Analysis.Theory: C, 40.8%; H, 5.2%; S, 26.7%. Found: C,40.6%; H, 5.11%; S, 27.15%.

25.7 parts of the tris-thiolacetate was suspended in ethanol and saturated with ammonia. The starting material dissolved and the product gradually crystallized out. Work up gave 14.0 parts (84% yield) of 98% pure 2,4,6- tris(mercaptomethyl) 1,3,5-trioxane.

Analysis.-Theory: C, 31.8%; H, 5.3%; S, 41.0%. Found: C, 33.3%; H, 5.7%; S, 42.1. Mercaptan, 1.29 eq./100 g.; theory, 1.31 eq./100 g.

Example III This example illustrates the preparation of 2,4,6-tris (mercaptomethyl) 1,3,5-trioxane by reacting the trimer of chloroacetaldehyde with sodium bisulfide under hydrogen sulfide pressure.

56 parts of aqueous sodium bisulfide was added to absolute ethanol to form a 50% solution. This mixture along with 39.25 parts of the chloroacetaldehyde trimer were charged to a pressure vessel. The vessel was then pressured up with hydrogen sulfide to a head pressure of about 80 p.s.i.g. The reaction mixture was brought up to a temperature of about 110 C. and kept there for about 36 hours (363 p.s.i.g. pressure). The vessel was then cooled, hydrogen sulfide bled ofi and the reaction mixture added to ether/water mixture and worked up as in the preceding example. The resulting product (82% yield) was a light clear liquid identified as 2,4,6-t'ris(mercaptomethyl) 1,3,5- trioxane.

Example IV This example illustrates the preparation of 2,4,6-tris (alpha,beta-dimercaptoethyl) 1,3,5-trioxane by reacting the dichloropropionaldehyde trimer with sodium thiolacetate and then treating the resulting product with ammonia.

110 parts of 2,4,6-tris(alpha,beta-dimercaptoethyl) 1,3, 5-trioxane are dissolved in 500 parts of acetonitrile. This mixture along with 162 parts of sodium thiolacetate is charged to a reaction flask equipped with stirrer, thermometer and nitrogen inlet. The mixture is brought to reflux under nitrogen and agitated at that temperature for about 50 hours. The reaction mixture is then cooled and ammonia bubbled in a room temperature until an excess of ammonia was present. The mixture is then allowed to stand at room temperature for about 3 days. The reaction mixture is then stripped to 40 C. 2 mm. The resulting product is combined with ether (200 parts), and then washed, dried, and stripped at 50 C. 2 mm. The resulting product is a viscous liquid which is identified as 2,4,6- tris alpha,beta-dirnercaptoethyl) 1,3,5-trioxane.

Example V This example illustrates the preparation and properties of 2,4,6-tris(beta-mercaptoethyl) 1,3,5-trithiane from the trimer of chlorothiopropionaldehyde.

150 parts of beta-chlorothiopropionaldehyde trimer, 200 parts of sodium thiolacetate and 600 parts of acetonitrile were added to a reaction flask and refluxed from 3.5 hours with agitation under nitrogen. The reaction mixture was then filtered to remove salts. The filtrate was stripped and stabilized at reduced pressure. The product was identified as the tri-thiolacetate derivative:

HQC HrS-ii-CHa 150 parts of the above-noted tri-thiolacetate was dissolved in parts of absolute alcohol. Ammonia was bubbled into the reaction mixture overnight at room tem perature. The mixture was stripped, filtered and dried. The product was a liquid identified as 2,4,6-tris(beta-mercaptoethyl) 1,3,5-trithiane:

s H s (JHzom-sH ExampleVI About 100 parts of polyether D, 22 parts of 2,4,6-tris (beta-mercaptoethyl) 1,3,5-trioxane produced above, 2 parts of tris(dimethylaminomethyl) phenol and 43 parts of 50/50 mixture toluene and methyl ethyl ketone were mixed together with stirring. The resulting fluid composition was spread out as a coating (about 2.5 mils thick) on tin panels. The coating was allowed to cure in air at 25 C. The properties of the resulting coating are as follows:

Example VII 100 parts of polyether A was combined with 60 parts of 1,3,5-tris(beta-mercaptoethyl) 2,4,6-trioxane and 2 parts of benzyldimethylamine and the mixture used as an adhesive for etched aluminum. The mixture was applied between two pieces of aluminum and the assembly cured at room temperature and at 100 C. The strengths of the bonds are indicated below:

Cured 2 hrs. 100 C., 5604 p.s.i. tensile shear. Cured 3 days at room temp, 1372 p.s.i. tensile shear.

13 Example VIII The adhesion shown in Example VI was also used to bond concrete to concrete The strengths are shown below:

P.s.i. Cured 48 hrs., room temp. (no catalyst) 528 Cured 48 hrs., room temp. 540

Cured 48 hrs., room temp. and soaked in water one week 422 All breaks were concrete failures rather than bond failures.

Example IX About 100 parts of polyether A was combined with 60 parts of 2,4,6-tris(beta-mercaptoethyl) 1,3,5-trioxane and 2 parts of tris(dimethylaminomethyl)phenol and the mixture spread out as a coating (about 3.0 mils thick) on tin panels. The coating was allowed to cure in air at 25 C. The films had good gloss and adhesion. The properties of the resulting coating are as follows:

Set to touch, min. 20 Cotton free, min. 25 Dry hard, min. 30 M3 in. mandrel flex test Passed Pencil hardness F Solvent, 15 min.:

Toluene Unchanged Methyl isobutylketone Unchanged Cold water, 24 hours Unchanged Aqueous NaOH, 60 min. Unchanged Example X About 100 parts of polyether B, 38 parts of 2,4,6-tris (beta-mercaptoethyl) 1,3,5-trioxane, 2 parts of tris(dimethylaminomethyl) phenol and 43 parts of 5 50 mixture of toluene and methyl ethyl ketne were mixed together with stirring. The resulting composition was spread out as a coating (about 2.5 mils thick) on tin panels. The coating was allowed to cure in air at 25 C. The films had excellent glass and appearance and good adhesion to the tin plates. The properties of the resulting coating are as follows:

Set to touch, min. 20 Cotton free, min 30 Dry hand, min. 40 in. mandrel flex test Passed Pencil hardness H-B Solvent, 15 min.:

Toluene Unchanged Methyl isobutylketone Unchanged Cold water, 24 hours Unchanged aqueous NaOH, 60 min Unchanged Example XI Example I is repeated with the exception that the betachloropropionaldehyde trimer is replaced with a mixed trimer of beta-chloropropionaldehyde and chloroacetaldehyde. Related results are obtained.

Example XII Example I is also repeated with the exception that the beta-chloropropionaldehyde trimer is replaced by a tetramer of beta-chloropropionaldehyde O-C-O Q l CICHzCHr-C H HC-CHzCH Ol 0 -o CHzCHgCl Related results are obtained.

Example XIII Example I is repeated with the exception that the betachloropropionaldehyde trimer is replaced by a mixed tetramer of beta-chloropropionaldehyde and beta-chlorothiopropionaldehyde. Related results are obtained.

14 Example XIV Examples I and V to VIII are repeated with the exception that the beta-chloropropionaldehyde trimer is replaced with 2,4,5-tri(beta-chloroethyl) 1,3-dioxalane. Related results are obtained.

Example XV Examples I and V to VIII are repeated with the excep tion that the beta-chloropropionaldehyde trimer is replaced with 2,4,5-tris(chloroethyl) 1-oxa-3,5-dithiane. Related results are obtained.

Example XVI This example illustrates the preparation of 2,4,6-tris (beta-mercaptoethyl) 1,3,5-trioxane using thiourea.

A reaction flask was charged with 167 parts of betachloropropionaldehyde trimer, 151 parts of thiourea, 300 parts distilled water and 300 parts of ethanol. The mixture was blanketed with nitrogen, stirred vigorously and heated to reflux until it became homogeneous (8 to 10 hours).

It was then heated for 2 to 3 additional hours and cooled to room temperature. The mixture was then saturated with ammonia (about 186 parts).

The mixture was stirred at 25 C. for 24 hours under nitrogen. The product came out as a lower oil layer. The bulk of the ammonia was stripped oil and the product taken up in 750 parts of ether. The ether was washed to neutrality with distilled water and dried. The dried ether layer was stripped to 50/ 1 mm. to yield 136 parts (84% yield) of colorless viscous liquid product identified as 2,4, 6-tris(beta-mercaptoethyl) 1,3,5-trioxane.

Alternatively, the solution of thiouronium salt was treated with 475 g. (1.98 mole) Na S-9 H O. Some NaCl comes out over a period of several hours. The mixture was stirred, under nitrogen, for several days and then saturated with "H 8 to spring TMT. The product was extracted into ether and worked up as above to yield 124 g. (77%) of the above-noted product.

The aqueous alcohol solution of NaCl and thiourea was concentrated on a thermosyphon evaporator to 550 C. and cooled to give NaCl and thiourea (274 g.). Recrystallization from methanol gave 93 g. (62% of 1.98 moles :used in reaction) of thiourea still containing ca. 13% NaCl. Further recrystallization gave 28 g. M.P. 177.5, mixed M.P. with thiourea 177179.

We claim as our invention:

1. A compound possessing one S-trioxane or S-trithane ring substituted in at least three different places on the ring with a --SH group or a mercapto-substituted alkyl group, which alkyl group contains only hydrogen and no more than six carbon atoms, the ring carbon atoms being also attached to hydrogen.

2. A 2,4,6-tris(mercaptoalkyl)trioxane wherein each alkyl group contains from 1 to '5 carbon atoms and is made up only of carbon and hydrogen.

3. A 2,4,6-tris(mercaptoalkyl)trithiane wherein each alkyl group contains from 1 to 5 carbon atoms and is made up only of carbon and hydrogen.

4. A compound of the formula RSH wherein Y is a member of the group consisting of oxygen and sulfur, R is a bivalent alkylene radical containing from 1 to 5 carbon atoms and being made up only of carbon and hydrogen and R is hydrogen.

5. 2,4,6-tris(beta-mercaptoethyl) 1,3,5-trioxane.

6. 2,4,6-tris(beta-mercaptoethyl) 1,3,5-trithiane.

7. 2,4,6-tris(mercaptomethyl) 1,3,5-trioxane.

8. 2,4,6-trismercapto 1,3,5-trioxane.

15 16 9. 2,4,6-trismercapto 1,3,5-trithiane. 5 carbon atoms and being made up only of carbon and 10. A compound of the formula hydrogen.

IIISH References Cited C 5 Houben-Weyl Methoder der Organischen Chemie, vol. IX, 1955 pages 7-10. l Reid Organic Chemistry of bivalent sulfur, vol. I, 1958 Chem. Pub. 00., N.Y., pages 29 and 30.

wherein R is an alkylene radical containing from 1 t0 JAMES A. PATTEN, Primary Examiner. 

